Cellulosic material



pounds of the general formula action of 'water by treating them with the' acid mental properties thereof I o r change in jg en'eral p ai ce- 1' "Treatin ce l losetextile materials with a 'lution 'of an 'aldehydo quaternfaryammonium compound of the above formula and heating the treated materialgabovej about 100 C.": ca'anuse'sv a Patented July 28,- 1942 PATE N T ""OFFICE CELLULOSIC Manama Y I 01.0111 ninocmq en iae, and Al annoukmhilae 1 pany, Philadelphia, Pa;

.Y. .j, This nive ti'dh concerns the 11r 1p rbye;iie11t gbf ,ceIIuloslcv materials; particularly celluloslc fibers,

' consisting ofaliphaticgroupsa'nd cycloaliphatic 115 hydrocarbon group's whenjtakensihgly and when taken together I divalent saturated aliphatiCh ra dicals which jointly with the nitrogenform a het- 'erocycle, R3 is a member ofthe grQuDconsistih of hydrogen and alkyl groups, R; is'a member of the class consistingpihydrogen and aliphatic. eerbm ps 5 s e.-, .1.

We have described 1 in application Serial No. 309,398; filed' December 15, 1939, how bolysaccharides may be rendered resistant to theusual 5 saltbf-ah aminomethyl aldehyde w e hav'e'now I found that'the aldehyde quaternaryfammonium compounds of the above'fformula are. even more efiective in rendering cellulose water resistant so I v that swelling of cellulose in films, or fibers and m n es in dimension of cellulose fabrics? are minimizedwithout loss of the essential fundareaction to occur between some of the hydroxylAo groups of the cellulose and the a1dehydo"quat-"' fompound, Thereby the nature emary j added from the'aldehydofquaternary ammonium compound possesses a. long "hydrocarbon chain, the surface of the fcellulosic material is rendered water-repellent, If the groups are small, the replacement of hydroxyl groups nevertheless renders the cellulosi'c material sufllciently hydroe J phobicvto. decrease the sensitivityof the material lio-v 2 to. water. As. a .result of -the reaction,v therefore, .c ellulosic fabrics become more stable in z-dimensionsthan' untreated fabric. v 1

. The aldehyde quaternary ammonium" compounds ofthe above formula are obtained as de- .55

scribed inapplication serial No; 1350134, filed August 2; 1940, by reacting a disubstituted aminoinethylaldehyde:of'theformula a v v f i he ha ome yli ther, of Iilrimari o Sec d- ;ary alcohol; having the r rmula nqcrhx {where ,it e symbols haye the same 'sig lflcanceas "above. The aminomethyl'aldehydes are formed by reacting such aldehydes as acetaldehyde, propionaldehyde, isobutyraldehyde,- valeraldehyde, dodecylaldehyde, 9,10-octadecenylaldehyde, octadecylaldehyde; etc. with formaldehyde and areactive "famine such"asdimethyIamineQ dibutylamina di- 'idine', etc; The ha'lom ethyl eat rs are obtaihed from such alcohols} as' methyl, ethylfi-butyl; oc'tyl,

decenyl, capryl, dicapr'yl; benzyl hexahydrobem z phenoxyethyl, etc. by' reacting them with mmai eh'yde and hydrogen chloride;

Typical f "the aldehydbquaternaryamenihali des 'wh i'chma'y be prepared a're the-folmmooum-Cm- CHQ Ethoxymethyl dimethyl B-r'riethyl-B-lormyl-propyl ammonium chloride CH1; I 'clmocriaN-gcn d ouo" Hap Cfapi-fylosjyinethyl p-formylefhyl diethyl ammonium chloride Cl OC:H4OCHi'-I ICH:CH-CHO C CH] HI Phenoxyethorymethyl fl-iorrnyl-propyl morpholinium chloride 0 c1 CilieO QH|l I-CH|,CKCHO i)! CuHa Butoxymethyldimethylp-iormyl-octadecyl ammonium chloride l Typical cellulosic textile materials include cotton, linen, regenerated cellulose, cellulose esters,

cellulose ethers, etc. in the form ofiibers, filaments, films, sheets, yarn, fabric. In this invention the use of any cellulosic textile material having free hydroxyl groups is contemplated.

Example 1 A piece iao x 80, 4 yaq as in. cotton sheeting wasflrmly clamped in a rigid frame and impregnated with a aqueous solution of the quaternary ammonium salt obtained from 2-ethyl hexoxymethyl chlq-ide and 'dimethylaminoneopentar nal .(2-ethyl hexoxymethyl dimethyl p-methyl-pformyl-propyl ammonium chloride). The cloth was dried at room temperature and then heated for one-half hour at 130 C. while stillin the frame. The piece of cloth was .removed' from the frame and carefully measured. It was then laundered in a hot solution-of soap and soda ash, rinsed, dried, and ironed. The dimensions of the piece of cloth were again determined. Shrinkage in the direction of the warp was 2.3%. The shrinkage of the original sheeting subjected to the same laundering process was 5.25%.

Example 2 salt obtained from benzyloxymethyl chloride and diethylaminoneopentanal (benzyloxymethyl diethyl p-methyl p-formyl-propyl ammonium chloride). Shrinkage along the warp direction was 1.96%.

Example 3 Another piece of the cotton sheeting was impregnated with a 10% aqueous solution of methallyloxymethyl dimethyl p-formyl-p-methyl-propyl ammonium chloride, following the same general procedure as described in Example 1. The

dried, impregnated fabric was heated for 35 minutes at l-l30 C. After the dimensions of the laundered as in Example 1. It was then found that shrinkage warp-wise was 0.98%.

treated cloth had been determined, the cloth was Example 4 A piece of the sheeting used in the above examples was clamped in the frame, immersed in a 10% aqueous solution of dodecyloxymethyl dimethyl p-methyl-pdormyl-prowl ammonium bromide, dried for five minutes in an oven at 127 C., and then heated in an oven at 150 C. for five minutes. The cloth was removed from the frame and laundered as in the preceding examples. Shrinkage along the warp was now only 1.84%

Example 5 A piece of the cotton sheeting already decarefully, dried, and ironed. The repellency was still very high.

Example 6 The'procedure of Example 5 was followed with a piece of spun rayon fabric. The treating agent was octadecyloxyme'thyl dimethyl fl-methyl-flfo'rmyl-propyl ammonium chloride. The treated cloth likewise possessed a water-repellent finish which: was fast to laundering.

Example 7 Kraft paper was impregnated with a 20% solu-' tion or dodecyloxymethyl dimethyl p-methyl-pformyl-propylammonium chloride- It was then placed ,in an oven at C. for forty minutes.

The resulting paper had an increased resistance to disintegration by water.

. Example 8 Example No. l'was repeated using cotton yarn. The resistance to shrinkage was greatly improved. y

The treating 0f cellulosic materials with an aldehyde quaternary ammonium halide followed by heating to cause a reaction between the cellulosic material and the halide yieldsa product which is less sensitive to water than untreated material. Woven fabric becomes resistant to changes in dimensions during washing. This effect may be utilized in conjunction with a mechanical shrinking procedure to give. superior, shrunk fabrics. If desired, the process of this invention may be'adapted to altering the surface of cottomrayon, linen, and the like so that fabricsof'these materials shed water. The reaction of long-chained groups with' cell'ulo'se gives a softening effect which is permanent.

Weclaim: J 1. A-method-for improving cellulosic textile materials having free hydroxyl groups which comprises treating said materials with a solution of a compound having the formula R1 ROClEi,;N-\.CHJJCHO R1 7 RI 4 wherein R is a member of the class consisting of aliphatic, arylaliphatic, and hydroarylaliphatic groups having at least one hydrogen on the carbon atom attached to the ether oxygen atom, R1 and R: are members of the class consisting of aliphatic groups and aliphatic hydrocarbon droxyl groups, which comprises impregnating said fibers with. a solution of a dodecyloxymethyl groups when taken singly and when taken together divalent saturated aliphatic radicals which Jointly with nitrogen form a heterocycle, R3 is a groups, and X is a halogen, and heating the treated materials between 100 C. and about 150 '2; A method for improving cellulosic textile fibers having free hydroxyl groups, which comprises treating said fibers with a solution of a compound having the formula ('31 R; ROCHr-N-CHz- --CHO OH: CH: R4

wherein R is a member of the class consisting of aliphatic, arylaliphatic, and hydroarylaliphatic groups having at least one hydrogen on the carbon atom attached to the ether oxygen atom, Ra is a member of the class consisting of hydrogen and alkyl groups, and R4 is a'member of the class consisting of hydrogen and aliphatic hydrocarbon groups, and heating the treated materials between about 100 C. and the decomposition temperature of the cellulosic material.

3. A method for increasing the water-resistance of cotton which comprises treating cotton with a solution of a compound having the formula wherein R is an aliphatic, hydrocarbon group having at least one hydrogen atom on the carbon atom attached to the ether, oxygen atom, R3 is a member of the class consisting of hydrogen and alkyl groups, and R4 is a member of the class consisting of hydrogen and aliphatic hydrocarbon groups, and heating the cotton between about 100 C. and about 175 C.

4. A method for increasing the water-resistance of cellulosic textile fibers having free hy- -CHO droxyl groups, which comprises treating said fibers with a solution of a compound having the formula wherein R is a member of the class consisting of aliphatic, arylaliphatic and hydroarylaliphatic groups having at least one hydrogen on the carbon atom attached to the ether oxygen atom, R: is a member of the class consisting of hydrogen and alkyl groups, and R4 is a member of the class consisting of hydrogen and aliphatic hydrocarbon groups. at least one of the groups R and R4 having more than 12 carbon atoms, andheatingthe treated materials between about 100 C. and the.

decomposition temperature of said cellulosic fibers.

5. A method for increasing the water-resistance of cellulosic textile fibers having free hydroxyl groups, which comprises impregnating said fibers with a solution of an alphyloxymethyl dimethyl fl-methyl-p-formyl-propyl ammonium chloride and heating the treated fibers above 100 C. but below the decomposition temperature of said fibers.

6. A method for imparting hydrophobic properties to cellulosic textile fibers having free hydimethyl ,B-formyl-fi-methyl-propyl ammonium chloride and heating the treatedfibers above 100 C.'but below the decomposition temperature of said fibers. I

7. A method for increasing the water-resistance of cellulosic textile fibers having free bydroxyl groups, which comprises impregnating said fibers with a solution of a butoxymethyl dimethyl fl-formyl-octadecyl ammonium chloride and heating the treated fibers above 100 C. but below the decomposition temperature of said fibers.

8. A method for stabilizing a woven cellulosic fabric which comprises impregnating said fabric with a solution of a butoxymethyl dimethyl pformyl-p-methyl-propyl ammonium halide and heating the impregnated fabric above 100 C. but

below the decomposition temperature of said fabric.

9. Hydroxyl-bearing cellulosic textile materials having hydroxyl groups reacted with a compound of the formula wherein R is an aliphatic, arylaliphatic, or hydroarylaliphatic group having at least one hydrogen on the carbon atom attached to the ether oxygen atom, R1 and R2 are members of the class consisting of aliphatic groups and cycloaliphatic hydrocarbon groups when taken singly and when taken together divalent saturated allwherein R is an aliphatic hydrocarbon group, having at least one hydrogen atom on the carbon atom attached to the ether oxygen atom, R3 is a member of the class consisting of hydrogen and alkyl groups, and R4 is a member of the class consisting of hydrogen and aliphatic hydrocar- ROCHr-N-CHz- CH0 CH: CH: 4

wherein R is an aliphatic hydrocarbon group having it 183st bn hydroz en stain. on

and alkylgroup's, and miss; member of tne'clzgsa consisting, of hydmgep gpd aliphatic I mm , ZL. Hon; 

